JPH1180986A - Removing copper from nickel chloride solution containing copper - Google Patents
Removing copper from nickel chloride solution containing copperInfo
- Publication number
- JPH1180986A JPH1180986A JP9254228A JP25422897A JPH1180986A JP H1180986 A JPH1180986 A JP H1180986A JP 9254228 A JP9254228 A JP 9254228A JP 25422897 A JP25422897 A JP 25422897A JP H1180986 A JPH1180986 A JP H1180986A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- nickel
- chloride solution
- leaching
- nickel chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銅を含有する例え
ばニッケルマットなどの金属硫化物を原料とし、塩素浸
出と電解採取によって電気ニッケルを回収するニッケル
電解精錬工程において、工程中に行われる含銅塩化ニッ
ケル溶液から銅を電解採取によって除去する脱銅電解工
程の改善に関するものである。The present invention relates to a nickel electrolytic refining process for recovering electric nickel by chlorine leaching and electrolytic extraction from a metal sulfide such as nickel matte containing copper as a raw material. The present invention relates to an improvement in a copper removal electrolytic process for removing copper from a copper nickel chloride solution by electrolytic extraction.
【０００２】[0002]
【従来の技術】従来、高純度ニッケルは、図２に代表さ
れる工程により製造されている。すなわち、図２に従っ
てその主要工程（ａ）〜（ｅ）について概要的に説明す
ると、該工程は、（ａ）含銅塩化ニッケル溶液中の銅を
ニッケルマット中のニッケルと置換反応させ、除銅塩化
ニッケル溶液（ＣＭＬ）と、含銅残渣（ＣＭＲ）を得る
セメンテーション（ＣＭ）工程、（ｂ）前記除銅塩化ニ
ッケル溶液（ＣＭＬ）中のコバルトなどの不純物をさら
に除去して、高純度塩化ニッケル溶液（純液）を得る浄
液工程、（ｃ）前記した高純度塩化ニッケル溶液を電解
液として用い、電解を行って高純度ニッケル（Ｅ−Ｎ
ｉ）を得るニッケル電解工程、を主要な工程とし、さら
に、（ｄ）工程（ａ）のセメンテーション（ＣＭ）工程
で得られた含銅残渣（ＣＭＲ）と、ニッケルマットを塩
素で浸出して濾過し、濾液として含銅塩化ニッケル溶液
（ＣＰＬ）、残渣としてさらなる濾過残渣（ＣＰＲ）を
得る浸出（ＣＰ）工程、（ｅ）工程（ｄ）で得られた含
銅塩化ニッケル溶液（ＣＰＬ）の一部を電解液として用
い、陽極に不溶性電極、陰極にチタン電極を用いて電解
して銅粉を得、電解廃液（ＣｕＬ）を工程（ｄ）に還流
させてセメンテーション（ＣＭ）工程に供給する脱銅電
解工程からなる。なお、工程（ｃ）のニッケル電解工程
で発生する塩素ガスは、電解廃液の脱塩素工程で得られ
た塩素ガスとともに塩素回収工程に送られ、回収された
塩素ガスは工程（ｄ）の浸出工程に送られ、また、脱塩
素電解廃液はニッケル原料ニッケルマットのスラリー化
のための破砕工程に供給される。2. Description of the Related Art Conventionally, high-purity nickel has been manufactured by a process represented by FIG. That is, the main steps (a) to (e) will be schematically described with reference to FIG. 2. In this step, (a) a copper-containing nickel chloride solution is subjected to a substitution reaction with nickel in a nickel mat to remove copper. A cementation (CM) step of obtaining a nickel chloride solution (CML) and a copper-containing residue (CMR); (b) further removing impurities such as cobalt in the copper-free nickel chloride solution (CML) to obtain a high-purity chloride; A purification step of obtaining a nickel solution (pure solution); (c) electrolysis is performed by using the above-mentioned high-purity nickel chloride solution as an electrolytic solution to obtain high-purity nickel (E-N
The nickel electrolysis step for obtaining i) is the main step, and the copper-containing residue (CMR) obtained in the cementation (CM) step of step (a) and the nickel mat are leached with chlorine. Filtration, a leaching (CP) step of obtaining a copper-containing nickel chloride solution (CPL) as a filtrate, a further filtration residue (CPR) as a residue, and (e) a copper-containing nickel chloride solution (CPL) obtained in step (d). A part is used as an electrolyte, electrolysis is performed using an insoluble electrode for the anode and a titanium electrode for the cathode to obtain copper powder, and the electrolytic waste liquid (CuL) is refluxed to the step (d) and supplied to the cementation (CM) step. Copper removal electrolytic process. The chlorine gas generated in the nickel electrolysis step of the step (c) is sent to the chlorine recovery step together with the chlorine gas obtained in the dechlorination step of the electrolytic waste liquid, and the recovered chlorine gas is subjected to the leaching step of the step (d). And the dechlorinated electrolytic waste liquid is supplied to a crushing step for slurrying nickel raw material nickel matte.
【０００３】本発明は、上記高純度電気ニッケル精錬工
程中、工程（ｅ）で行われる脱銅電解工程の改善に係る
ものであり、該工程において銅を効率的に除去する方法
を提案するものであり、以下により詳細に説明する。高
純度電気ニッケル精錬工程中における脱銅電解工程の意
義について説明すると、図２および図３に示すように、
工程（ａ）のセメンテーション工程で得られた含銅残渣
はニッケルマットスラリーの一部と混合されて塩素で浸
出されるが、ニッケルマット中に含まれる銅は塩素浸出
液中で銅イオンとなって系内に蓄積される。本発明にお
いて対象とする脱銅電解工程はこの蓄積された余剰の銅
を銅粉として除去回収することを目的とする工程であ
る。[0003] The present invention relates to the improvement of the copper removal electrolysis step performed in the step (e) during the high purity electric nickel refining step, and proposes a method for efficiently removing copper in the step. And will be described in more detail below. The significance of the copper removal electrolysis step in the high-purity electric nickel refining step will be described. As shown in FIGS.
The copper-containing residue obtained in the cementation step of step (a) is mixed with a part of the nickel matte slurry and leached with chlorine, but the copper contained in the nickel matte becomes copper ions in the chlorine leaching solution. Accumulated in the system. The copper removal electrolytic process targeted in the present invention is a process aimed at removing and collecting the accumulated excess copper as copper powder.
【０００４】脱銅電解工程の設備フローを図４に示す
と、工程（ｄ）の浸出（ＣＰ）工程で得られた含銅塩化
ニッケル溶液（ＣＰＬ）の一部を受入槽１に導入し、ニ
ッケル電解工程からの電解廃液（アノライト）により含
銅塩化ニッケル溶液（ＣＰＬ）中の銅濃度を所定の基準
値になるように希釈し、ヘッドタンク２から脱銅電解槽
３に給液する。給液の一部はカソライトとして電解槽３
よりオーバーフローさせて液面を一定に保持する。電解
槽３内のアノードボックス４から塩素ガスと廃液を同時
に吸引し、気液分離器５で塩素ガスと廃液を分離し、塩
素ガスはバッファータンク６を経て浸出（ＣＰ）工程に
還流させる。一方廃液は、廃液槽７を経てカソライト中
継槽８に送られ、そこで廃液中の遊離塩素は、カソライ
ト中の１価銅イオンにより還元処理されてセメンテーシ
ョン（ＣＭ）工程に還流される。FIG. 4 shows the equipment flow of the copper removal electrolysis step. A part of the copper-containing nickel chloride solution (CPL) obtained in the leaching (CP) step of the step (d) is introduced into the receiving tank 1. The copper concentration in the copper-containing nickel chloride solution (CPL) is diluted with an electrolytic waste solution (anolyte) from the nickel electrolysis process so as to have a predetermined reference value, and the diluted copper solution is supplied from the head tank 2 to the copper removal electrolytic bath 3. Part of the liquid supply is catholyte and used in electrolytic cell 3.
The liquid surface is kept constant by overflowing more. The chlorine gas and the waste liquid are simultaneously sucked from the anode box 4 in the electrolytic cell 3, the chlorine gas and the waste liquid are separated by the gas-liquid separator 5, and the chlorine gas is returned to the leaching (CP) step via the buffer tank 6. On the other hand, the waste liquid is sent to a catholyte relay tank 8 via a waste liquid tank 7, where free chlorine in the waste liquid is reduced by monovalent copper ions in the catholyte and returned to a cementation (CM) step.
【０００５】一方、電解槽３のカソード９に電着した銅
粉は、例えばエアーシリンダーを用いたビーム落下方式
などの分離手段でカソードから分離され、レパルプ槽１
０、レパルプ中継槽１１を経て、遠心分離機１２で濾
過、洗浄後系外に排出される。濾液は濾液槽１３、１４
を経てその大部分は電解槽３に還流する。On the other hand, the copper powder electrodeposited on the cathode 9 of the electrolytic cell 3 is separated from the cathode by a separating means such as a beam dropping method using an air cylinder.
After passing through the repulp relay tank 11, it is filtered by the centrifugal separator 12, washed and discharged out of the system. The filtrate is in filtrate tanks 13 and 14
Most of the water is returned to the electrolytic cell 3 via.
【０００６】表１は、脱銅電解工程に使用される含銅塩
化ニッケル溶液（ＣＰＬ）、電解廃液（アノライト）及
び銅濃度希釈後の給液の液組成の一例を示すものであ
る。Table 1 shows an example of the composition of the copper-containing nickel chloride solution (CPL), the electrolytic waste solution (anolyte), and the feed solution after the dilution of the copper concentration, which are used in the copper removal electrolytic process.
【０００７】[0007]
【表１】 [Table 1]
【０００８】脱銅電解工程は以上のフローにより行われ
ているが、従来脱銅電解工程に供給される含銅塩化ニッ
ケル溶液（ＣＰＬ）は、塩素を使用した浸出（ＣＰ）工
程後の浸出液であるためにｐＨが低く、かつ酸化性が高
かった。したがって電解槽３で起こるカソード反応（銅
の還元析出反応）は阻害され、電流効率を悪化させたり
するのでランニングコストが上昇するという問題があっ
た。[0008] The copper removal electrolysis step is performed according to the above flow. However, the copper-containing nickel chloride solution (CPL) conventionally supplied to the copper removal electrolysis step is a leachate obtained after the leaching (CP) step using chlorine. For this reason, the pH was low and the oxidizing property was high. Therefore, the cathode reaction (reduction and precipitation reaction of copper) occurring in the electrolytic cell 3 is hindered, and the current efficiency is deteriorated.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、ニッケルの
電解精錬の脱銅電解工程における上記の問題点を解決
し、脱銅電解の電流効率の向上と、これによるランニン
グコストの低減を図ることのできる含銅塩化ニッケル溶
液からの銅の除去方法を提供することを目的とするもの
である。SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems in the copper removal electrolytic process of nickel electrolytic refining, to improve the current efficiency of the copper removal electrolytic process, and to reduce the running cost. It is an object of the present invention to provide a method for removing copper from a copper-containing nickel chloride solution that can be performed.
【００１０】[0010]
【課題を解決するための手段】上記の目的を達成するた
めの本発明は、銅を含有する金属硫化物を原料とし、ニ
ッケルの塩素浸出を行い、これにより得られた塩化ニッ
ケル溶液からニッケルの電解採取を行うニッケル精錬方
法における脱銅電解工程において、含銅塩化ニッケル溶
液中の銅イオンを還元し、２価銅比を低下させた後に、
銅を電解採取する含銅塩化ニッケル溶液からの銅の除去
方法を特徴とするものであり、前記還元剤として金属ニ
ッケルを用いることが好ましい。In order to achieve the above object, the present invention provides a method for leaching nickel from a metal sulfide containing copper as a raw material, and removing nickel from the resulting nickel chloride solution. In the copper removal electrolysis step in the nickel refining method for performing electrowinning, after reducing copper ions in the copper-containing nickel chloride solution and reducing the bivalent copper ratio,
The method is characterized by a method for removing copper from a copper-containing nickel chloride solution for electrolytically collecting copper, and it is preferable to use metallic nickel as the reducing agent.
【００１１】[0011]
【発明の実施の形態】通常脱銅電解工程に供給される含
銅塩化ニッケル溶液（ＣＰＬ）中の銅イオンは１価およ
び２価の形態で存在している。脱銅電解に際しては、下
記に示す（１）式と（２）式の電解反応が起こる。 Ｃｕ２＋＋ｅ−＝Ｃｕ＋ （１） Ｃｕ＋ ＋ｅ−＝Ｃｕ （２） このうち（１）式の反応が優先的に進行するために、全
銅中の２価の銅イオンが占める割合、すなわちＣｕ２＋
／全Ｃｕ（以下、２価銅比という。）が高くなると、銅
粉の電解採取に使用される電力が余分にかかることにな
り、２価銅換算での脱銅電解のカソード電流効率の低下
を招くことになる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Copper ions in a copper-containing nickel chloride solution (CPL) usually supplied to a copper-free electrolytic process exist in monovalent and divalent forms. At the time of copper-free electrolysis, the following electrolytic reactions (1) and (2) occur. Cu 2+ + e − = Cu + (1) Cu + + e − = Cu (2) Among these, since the reaction of the formula (1) proceeds preferentially, the proportion of divalent copper ions in the total copper, that is, Cu 2+
When the total Cu (hereinafter, referred to as divalent copper ratio) is increased, an extra electric power used for electrowinning copper powder is required, and the cathode current efficiency of copper-free electrolysis in terms of divalent copper is reduced. Will be invited.
【００１２】上記した含銅塩化ニッケル溶液（ＣＰＬ）
中の２価銅比を支配するのが、工程（ｄ）の浸出（Ｃ
Ｐ）工程での反応条件の１つである酸化還元電位（ＯＲ
Ｐ；Ａｇ／ＡｇＣｌ電極）であり、図５に示すように酸
化還元電位（ＯＲＰ）が上昇すると２価銅比が上昇す
る。そして酸化還元電位（ＯＲＰ）と脱銅電解のカソー
ド電流効率の関係は、図６に示すように逆比例の関係、
すなわち酸化還元電位（ＯＲＰ）が上昇するとカソード
電流効率が低下することになる。The above copper-containing nickel chloride solution (CPL)
It is the leaching (C) in step (d) that governs the bivalent copper ratio in the
Oxidation-reduction potential (OR
P; Ag / AgCl electrode), and as shown in FIG. 5, when the oxidation-reduction potential (ORP) increases, the divalent copper ratio increases. As shown in FIG. 6, the relationship between the oxidation-reduction potential (ORP) and the cathode current efficiency of the copper removal electrolysis is inversely proportional,
That is, as the oxidation-reduction potential (ORP) increases, the cathode current efficiency decreases.
【００１３】より具体的には、例えば脱銅電解のカソー
ド電流効率１００％以上を達成するための酸化還元電位
（ＯＲＰ）は図５より４７８ｍＶ以下であることが必要
であり、この４７８ｍＶに対応する含銅塩化ニッケル溶
液（ＣＰＬ）中の２価銅比は図５より４８％付近である
ことがわかる。したがって、脱銅電解工程においては、
工程（ｄ）の浸出（ＣＰ）工程での反応条件の１つであ
る酸化還元電位（ＯＲＰ）が低いほど、すなわち工程
（ｄ）の浸出（ＣＰ）工程で得られた含銅塩化ニッケル
溶液（ＣＰＬ）中の２価銅比が低いほど高電流効率が得
られることになるが、一方において、浸出（ＣＰ）工程
において酸化還元電位（ＯＲＰ）を低くすることは、本
来の目的である原料ニッケルマット中のニッケルの浸出
を妨げる結果となってニッケルの生産効率上好ましくな
い。More specifically, for example, the oxidation-reduction potential (ORP) for achieving a cathode current efficiency of 100% or more in the copper removal electrolysis is required to be 478 mV or less from FIG. 5, which corresponds to this 478 mV. FIG. 5 shows that the ratio of divalent copper in the copper-containing nickel chloride solution (CPL) is around 48%. Therefore, in the copper removal electrolytic process,
The lower the oxidation-reduction potential (ORP), which is one of the reaction conditions in the leaching (CP) step of step (d), that is, the copper-containing nickel chloride solution obtained in the leaching (CP) step of step (d) ( The lower the ratio of divalent copper in CPL), the higher the current efficiency can be obtained. On the other hand, the lowering of the oxidation-reduction potential (ORP) in the leaching (CP) step is the original purpose of the raw material nickel. As a result, the leaching of nickel in the mat is prevented, which is not preferable in terms of nickel production efficiency.
【００１４】図７に、浸出（ＣＰ）工程でのニッケルの
浸出状態の指標である浸出後の濾過残渣（ＣＰＲ）中の
残留ニッケル品位と酸化還元電位（ＯＲＰ）との関係を
示したが、図７に見られるように酸化還元電位（ＯＲ
Ｐ）が低くなればなるほど濾過残渣（ＣＰＲ）中の残留
ニッケル品位が高くなり、ニッケルの浸出率が低下する
ことがわかる。したがって、脱銅電解工程でのカソード
電流効率の向上と浸出（ＣＰ）工程でニッケル浸出率の
向上とは、相反する関係にあるので両者を同時に満足さ
せることは困難であった。FIG. 7 shows the relationship between the residual nickel quality in the filtered residue (CPR) after leaching, which is an indicator of the state of leaching of nickel in the leaching (CP) step, and the oxidation-reduction potential (ORP). As shown in FIG. 7, the oxidation-reduction potential (OR
It can be seen that the lower the P), the higher the residual nickel quality in the filtration residue (CPR), and the lower the nickel leaching rate. Therefore, it is difficult to satisfy both of the improvement of the cathode current efficiency in the copper removal electrolysis step and the improvement of the nickel leaching rate in the leaching (CP) step at the same time, since they are opposite to each other.
【００１５】以上述べたように、浸出（ＣＰ）工程での
酸化還元電位（ＯＲＰ）は、前述の通りニッケルマット
中のニッケル等の金属の浸出率に大きな影響を及ぼすこ
とから、浸出（ＣＰ）工程で得られた含銅塩化ニッケル
溶液（ＣＰＬ）中の２価銅比を低く抑えるための反応条
件である酸化還元電位（ＯＲＰ）を低くするのには限界
がある。本発明者らは、脱銅電解工程への供給直前の含
銅塩化ニッケル溶液（ＣＰＬ）に、還元剤を用いて強制
的に２価の銅を１価の銅、または金属銅に還元させてや
れば、浸出（ＣＰ）工程でのニッケルの浸出率を低下さ
せることなく、脱銅電解でのカソード電流効率を高める
ことができるものとの考察に基づき本発明を完成したも
のである。As described above, since the oxidation-reduction potential (ORP) in the leaching (CP) step has a large effect on the leaching rate of a metal such as nickel in the nickel mat as described above, the leaching (CP) There is a limit to reducing the oxidation-reduction potential (ORP), which is a reaction condition for keeping the ratio of divalent copper in the copper-containing nickel chloride solution (CPL) obtained in the process low. The present inventors forcibly reduced divalent copper to monovalent copper or metallic copper by using a reducing agent in the copper-containing nickel chloride solution (CPL) immediately before the supply to the copper removal electrolytic process. The present invention has been completed based on the consideration that the cathode current efficiency in copper removal electrolysis can be increased without lowering the leaching rate of nickel in the leaching (CP) step.
【００１６】本発明において使用される還元剤は、工程
内に無用の不純物を増大させることがなく、また原料費
などのランニングコストをできるだけ抑えることのでき
るものを選択することが望ましく、この意味で例えば工
程内で発生する電気ニッケル屑を採用することが好まし
い。As the reducing agent used in the present invention, it is desirable to select a reducing agent which does not increase unnecessary impurities in the process and can minimize running costs such as raw material costs. For example, it is preferable to use electric nickel scrap generated in the process.
【００１７】[0017]
【実施例】本発明の実施例においては、図１に示すよう
な脱銅電解槽１槽を有するパイロット電解装置を用いて
脱銅電解実験を行った。図１において、３は脱銅電解
槽、１５はカラム槽、１６はストレーナー、１７は給液
流量調整用バルブである。この実施例においては含銅塩
化ニッケル溶液（ＣＰＬ）に相当する組成の給液を一旦
電気ニッケル屑片の入ったカラム槽へ通液し、給液中の
２価銅または１価銅とニッケルとを置換させ、１価銅ま
たは金属銅に還元した後、脱銅電解槽へ供給する方法を
用いた。実験条件を表２に示す。EXAMPLE In an example of the present invention, a copper removal electrolysis experiment was performed using a pilot electrolytic apparatus having one copper removal electrolytic bath as shown in FIG. In FIG. 1, reference numeral 3 denotes a copper removal electrolytic bath, 15 denotes a column bath, 16 denotes a strainer, and 17 denotes a liquid supply flow rate adjusting valve. In this embodiment, a feed solution having a composition corresponding to a copper-containing nickel chloride solution (CPL) is once passed through a column tank containing scraps of electric nickel, and copper (II) or monovalent copper and nickel in the feed are mixed with nickel. , And reduced to monovalent copper or metallic copper, and then supplied to a copper-free electrolytic cell. Table 2 shows the experimental conditions.
【００１８】[0018]
【表２】 カラム槽容量 ：３７．５リットル カラム給液流量 ：１．０リットル／ｍｉｎ 給液滞留時間 ：３７．５ｍｉｎ 還元剤 ：電気ニッケル屑片（900x25x1.2)(mm) 還元剤装入量 ：５０．０ｋｇ[Table 2] Column tank capacity: 37.5 liters Column supply flow rate: 1.0 liter / min Supply liquid residence time: 37.5 min Reducing agent: Electric nickel scrap (900x25x1.2) (mm) Amount: 50.0kg
【００１９】実験データの採取項目は、カラム槽給液
（入口側）およびオーバーフロー液（出口側）の酸化還
元電位（ＯＲＰ）と２価銅比、電気ニッケル屑片の消費
量およびカラム槽底にて採取された析出物の化学分析値
である。The collection items of the experimental data were the oxidation-reduction potential (ORP) and the ratio of copper (II) of the column tank feed (inlet side) and overflow solution (outlet side), the consumption of electric nickel debris, and the column tank bottom. It is a chemical analysis value of the precipitate collected by the above method.
【００２０】実験結果を表３に示す。Table 3 shows the experimental results.
【００２１】[0021]
【表３】 カラム槽給液（入口側） オーバーフロー液（出口側） 効果 ──────────────────────────────────── ORP pH 全Cu Cu2+ 2価銅 ORP pH 全Cu Cu2+ 2価銅 2価銅比 (mV) (g/l) (g/l) 比 (%) (mV) (g/l) (g/l) 比 (%) 減 (%) ──────────────────────────────────── 428 0.84 40.4 18.1 44.8 418 0.89 40.3 11.4 35.4 9.4 440 0.89 39.5 18.1 45.8 420 0.96 39.5 11.6 29.1 16.7 420 1.05 33.8 18.1 53.6 410 1.18 33.4 13.1 39.2 14.4 410 1.42 34.4 14.8 43.0 394 1.47 34.0 10.5 30.9 12.2 407 1.39 32.6 12.5 38.3 390 1.57 32.6 9.2 28.2 10.1 400 1.35 33.2 12.1 36.4 380 1.43 34.1 9.2 27.0 9.4 ────────────────────────────────────[Table 3] Column tank liquid supply (inlet side) Overflow liquid (outlet side) Effect ─────────────────────────────── ───── ORP pH Total Cu Cu 2+ Divalent Copper ORP pH Total Cu Cu 2+ Divalent Copper Divalent Copper Ratio (mV) (g / l) (g / l) Ratio (%) (mV) ( g / l) (g / l) Ratio (%) Decrease (%) ───────────────────────────────── ─── 428 0.84 40.4 18.1 44.8 418 0.89 40.3 11.4 35.4 9.4 440 0.89 39.5 18.1 45.8 420 0.96 39.5 11.6 29.1 16.7 420 1.05 33.8 18.1 53.6 410 1.18 33.4 13.1 39.2 14.4 410 1.42 34.4 14.8 43.0 394 1.47 34.0 10.5 30.9 12.2 407 1.39 32.6 12.5 38.3 390 1.57 32.6 9.2 28.2 10.1 400 1.35 33.2 12.1 36.4 380 1.43 34.1 9.2 27.0 9.4 ─────────────────────────────── ─────
【００２２】表３の結果から、カラム槽の入口側と出口
側で給液の酸化還元電位（ＯＲＰ）の差は１０〜２０ｍ
Ｖであり、図５に示された相関係数ｙより算出すると、
液中のＣｕの２価銅比を約１４％減少させることができ
ることがわかった。すなわち、図５および図６から脱銅
電解のカソード電流効率を７％上昇させることができ
た。From the results shown in Table 3, the difference in the oxidation-reduction potential (ORP) of the feed solution between the inlet side and the outlet side of the column tank is 10 to 20 m.
V, calculated from the correlation coefficient y shown in FIG.
It was found that the divalent copper ratio of Cu in the liquid could be reduced by about 14%. That is, from FIGS. 5 and 6, the cathode current efficiency of the copper removal electrolysis was increased by 7%.
【００２３】以上の実施例による実験操業を９日間継続
して行ったところ、カラム槽中の電気ニッケルは５４ｋ
ｇから２２ｋｇまで減少し、消費された電気ニッケル屑
片の量は３．５ｋｇ／日であった。カラム槽底に析出し
た沈殿物の分析結果を脱銅電解によって得られた銅粉の
分析結果と比較して表４に示す。When the experimental operation according to the above embodiment was continued for 9 days, the electric nickel in the column tank was 54 kN.
g to 22 kg, and the amount of spent electric nickel debris was 3.5 kg / day. Table 4 shows the results of analysis of the precipitate deposited at the bottom of the column tank in comparison with the results of analysis of copper powder obtained by copper-free electrolysis.
【００２４】[0024]
【表４】 [Table 4]
【００２５】表４の結果から、カラム槽底に得られる沈
殿物は、脱銅電解によって得られた銅粉とほぼ同等の組
成を示すことがわかった。これよりカラム槽内では、ニ
ッケル屑片の存在により給液中の銅がＣｕ２＋→Ｃｕ＋
→Ｃｕの還元反応を起こすほどの強い還元力を受けるこ
とがわかった。From the results shown in Table 4, it was found that the precipitate obtained at the bottom of the column tank had almost the same composition as the copper powder obtained by the copper removal electrolysis. Thus, in the column tank, the copper in the liquid supply was changed from Cu 2+ → Cu + due to the presence of the nickel scrap pieces.
→ It was found that the steel sheet received a strong reducing power enough to cause a reduction reaction of Cu.
【００２６】さらに、この実施例において、電解液のカ
ラム槽内での滞留時間を長くしたり、給液と電気ニッケ
ル屑片との接触面積を大きくしたり、あるいは電気ニッ
ケル屑片に振動を与え物質移動を促進するなどの方法を
採るときには、上記Ｃｕ２＋→Ｃｕ＋→Ｃｕの還元反応
はさらに促進され、一層２価銅比の減少による脱銅電解
におけるカソード電流効率の向上を図ることができるこ
とが実験的に確認された。Furthermore, in this embodiment, the residence time of the electrolytic solution in the column tank is increased, the contact area between the supply liquid and the electric nickel scraps is increased, or vibration is applied to the electric nickel scraps. When a method such as promoting mass transfer is employed, the above-mentioned reduction reaction of Cu 2+ → Cu + → Cu is further promoted, and the cathode current efficiency in the copper removal electrolysis can be further improved by reducing the divalent copper ratio. Was confirmed experimentally.
【００２７】[0027]
【発明の効果】以上述べたように、本発明の方法による
ときは、高純度ニッケルの電解精錬工程における含銅ニ
ッケル水溶液からの銅の除去を行うに際し、浸出（Ｃ
Ｐ）工程でのニッケルマット中のニッケルの浸出を阻害
することなく、換言すれば高いニッケルの生産効率を維
持しつつ、含銅塩化ニッケル溶液（ＣＰＬ）中の２価銅
比を低減させることができ、これによって脱銅電解の電
流効率の向上とこれによるランニングコストの低減を図
ることができるのでその効果は大きい。As described above, according to the method of the present invention, when copper is removed from the aqueous copper-containing nickel solution in the high-purity nickel electrolytic refining process, leaching (C
It is possible to reduce the divalent copper ratio in the copper-containing nickel chloride solution (CPL) without inhibiting the leaching of nickel in the nickel matte in the step P), in other words, while maintaining high nickel production efficiency. As a result, the current efficiency of the copper removal electrolysis can be improved and the running cost can be reduced, and the effect is great.
【図１】本発明の実施例に使用する実験用脱銅電解装置
の概略を示す斜視図である。FIG. 1 is a perspective view schematically showing an experimental copper removal electrolytic apparatus used in an embodiment of the present invention.
【図２】高純度ニッケル精錬のプロセスフロー図であ
る。FIG. 2 is a process flow chart of high-purity nickel refining.
【図３】脱銅電解工程の意義を示すための説明図であ
る。FIG. 3 is an explanatory diagram showing the significance of a copper removal electrolytic process.
【図４】脱銅電解工程における装置のフロー図である。FIG. 4 is a flow chart of an apparatus in a copper removal electrolytic process.
【図５】浸出（ＣＰ）工程での酸化還元電位（ｍＶ；Ａ
ｇ／ＡｇＣｌ電極）と浸出反応液中の２価銅比（％）と
の関係を示す相関図である。FIG. 5: Redox potential (mV; A) in the leaching (CP) step
g / AgCl electrode) and a divalent copper ratio (%) in the leaching reaction solution.
【図６】浸出（ＣＰ）工程での酸化還元電位（ｍＶ；Ａ
ｇ／ＡｇＣｌ電極）と脱銅電解工程におけるカソード電
流効率との関係を示す相関図である。FIG. 6: Redox potential (mV; A) in leaching (CP) step
FIG. 4 is a correlation diagram showing the relationship between the g / AgCl electrode) and the cathode current efficiency in the copper removal electrolytic process.
【図７】浸出（ＣＰ）工程での酸化還元電位（ｍＶ；Ａ
ｇ／ＡｇＣｌ電極）と該工程で得られる濾過残渣（ＣＰ
Ｒ）中の残留ニッケル品位との関係を示す相関図であ
る。FIG. 7: Redox potential (mV; A) in leaching (CP) step
g / AgCl electrode) and the filtration residue (CP
It is a correlation figure showing the relation with residual nickel grade in R).
１ 受入槽 ２ ヘッドタンク ３ 脱銅電解槽 ４ アノードボックス ５ 気液分離器 ６ バッファータンク ７ 廃液槽 ８ カソライト中継槽 ９ カソード １０ レパルプ槽 １１ レパルプ中継槽 １２ 遠心分離機 １３、１４ 濾液槽 １５ カラム槽 １６ ストレーナー １７ 給液流量調整用バルブ。 DESCRIPTION OF SYMBOLS 1 Receiving tank 2 Head tank 3 Copper removal electrolytic tank 4 Anode box 5 Gas-liquid separator 6 Buffer tank 7 Waste liquid tank 8 Catholite relay tank 9 Cathode 10 Repulp tank 11 Repulp relay tank 12 Centrifugal separator 13, 14 Filtrate tank 15 Column tank 16 Strainer 17 Valve for adjusting liquid supply flow rate.
Claims (2)
ッケルの塩素浸出を行い、これにより得られた塩化ニッ
ケル溶液からニッケルの電解採取を行うニッケル精錬方
法における脱銅電解工程において、含銅塩化ニッケル溶
液中の銅イオンを還元して２価銅比を低下させた後に、
銅を電解採取することを特徴とする含銅塩化ニッケル溶
液からの銅の除去方法。1. A copper-removing electrolysis step in a nickel refining method in which nickel leaching is performed using a metal sulfide containing copper as a raw material and nickel is extracted from a nickel chloride solution obtained thereby. After reducing copper ions in the nickel chloride solution to reduce the divalent copper ratio,
A method for removing copper from a copper-containing nickel chloride solution, comprising electrolytically collecting copper.
ことを特徴とする請求項１記載の含銅塩化ニッケル溶液
からの銅の除去方法。2. The method for removing copper from a copper-containing nickel chloride solution according to claim 1, wherein metallic nickel is used as the reducing agent.
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|---|---|---|---|
| JP25422897A JP3427879B2 (en) | 1997-09-03 | 1997-09-03 | Method for removing copper from copper-containing nickel chloride solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25422897A JP3427879B2 (en) | 1997-09-03 | 1997-09-03 | Method for removing copper from copper-containing nickel chloride solution |
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| Publication Number | Publication Date |
|---|---|
| JPH1180986A true JPH1180986A (en) | 1999-03-26 |
| JP3427879B2 JP3427879B2 (en) | 2003-07-22 |
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ID=17262050
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25422897A Expired - Fee Related JP3427879B2 (en) | 1997-09-03 | 1997-09-03 | Method for removing copper from copper-containing nickel chloride solution |
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| Country | Link |
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